Chloroxysulfurpentafluoride and derivatives thereof

ABSTRACT

THE COMPOUNDS CHLOROXYSULFURPENTAFLUORIDE AND PENTAFLUOROSULFUR CHLOROFORMATE ARE PROVIDED. THESE COMPOUNDS ARE USEFUL AS POLYMERIZATION INITIATORS FOR FLUOROLEFINS. A METHOD IS ALSO PROVIDED FOR PREPARING CHLOROXYSULFURPENTAFLUORIDE BY REACTING THIONYL TETRAFLUORIDE AND CHLORINE MONOFLUORIDE IN THE PRESENCE OF POTASSIUM FLUORIDE, RUBIDIUM FLUORIDE, OR CESIUM FLUORIDE. THE COMPOUNDS PENTAFLUOROSULFURCHLOROFORMATE, PENTAFLUOROSULFUROXYDIFLUORAMINE AND PENTAFLUOROSULFURPEROXIDE ARE PREPARED BY REACTING CHLOROXYSULFURPENTAFLUORIDE WITH CARBON MONOXIDE, DINITROGEN TETRAFLUORIDE AND SULFUR MONOXIDE PENTAFLUORIDE, RESPECTIVELY.

June 1, 1971 c, JTSCHACKY EI'AL 3,582,292

- -'CHLOROXYSULFURPENTAFLUORIDE AND nmmvuxvss. THEREOF Filed Sept. 27. 1968 FLOW DIAGRAM OF THE PROCESS J, I I I, l

CARBON J DINITROGEN OLEF/N SULFUR MONOXIDE MONOXIDE TETRAFLUORIDE BOND PENTAFLUORIDE ULTRA VIOLET ULTRA VIOLET ULTRA VIOLET ULTRA VIOLET RADIATION RADIATION RADIATION RADIATION PENTAFLUORIDE PENTAFLUORIDE FLUORNATED PENTAFLUORIDE SULFUR SULFUR OXY- OLEFIN SULFUR FORMATES AMINEFLUORIDES COMPOUND PEROXIDES INVENTORS. C. J. SCHACK B R. D. WILSON 4 1. ldzz;

ATTORNEY United States Patent Cfice 3,582,292 Patented June 1, 1971 3,582,292 CHLOROXYSULFURPENTAFLUORIDE AND DERIVATIVES THEREOF Carl J. Schack, Chatsworth, and Richard D. Wilson,

Canoga Park, Califi, assignors to North American Rockwell Corporation Filed Sept. 27, 1968, Ser. No. 763,141 Int. Cl. C01b 17/45; C07c 161/00 US. Cl. 23-367 3 Claims ABSTRACT OF THE DISCLOSURE BACKGROUND OF THE INVENTION The invention herein described was made in the course of or under a contract with the Department of the Navy.

This invention relates to the new compound chloroxysulfurpentafluoride -(SF OCl) which is prepared in nearly quantitative yields by reacting chlorine monofiuoride (ClF) and thionyl tetrafluoride (S01 in the presence of a member selected from the group consisting of potassium fluoride (KF), rubidium fluoride (RbF) and cesium fluoride (CsF). The newly formed SF OCI, because of the high reactivity of its ClO bond is a reactive source for the introduction of the SF O group into organic compounds. For example, pentafluorosulfur chloroformate [SF OC(O)Cl] can be prepared by reacting SF OCI with carbon monoxide (CO) in the presence of ultra violet light to give the desired reaction product. Other compounds that can be prepared according to the lattter reaction are pentafluorosulfurperoxide (SF OOSF and pentafiuorosulfur oxydifluoramine (SF ONF SUMMARY OF THE INVENTION Synthesis of the new compound, chloroxysulfurpentafluoride can be accomplished by means of the alkali metal fluoride catalyzed addition of ClF to S01 at 40 to -78 C. The synthesis can be represented by the chemical equation MF s01. 01F sF5001 where M is K, Cs, or Rb. The compound SF OCl can be photochemically reacted to give SF OOSF according to the equation 11V 11V SFsOCl SF5O Cl; 2SF5O SFBOOSF The compound SF ON=F can also be prepared from SF OCl according to the equation SF5OO1 %N F4 SF5ONF2 M312 The compound SF OC(O)C1 can be prepared from SF O C1 by the reaction In the above equation uv represents ultra violet radiation.

DESCRIPTION OF PREFERRED EMBODIMENT The synthetic reactions employed here were usually conducted in stainless steel cylinders and the newly formed products were separated and purified using a stainless steel-Teflon vacuum line. The reported pressures were measured by means of a commercially available Heise, Bourdon tube type, pressure gauge. Infrared spectra were taken on Perkin-Elmer Infracords 137 and 337 using 5 cm. path length stainless steel or Kel-F cells fitted with AgCl windows. The F n.m.r. spectra were obtained at 40 C. using a Varian Associates high resolution n.m.r. spectrometer operating at 56.4-mc. Samples were sealed in Pyrex tubes with CFCl as the internal standard. Mass spectral data were obtained with a conventional mass spectrometer.

The chlorine monofluoride employed herein was prepared by heating an equimolar mixture of chlorine and fluorine to C. for several hours in a stainless steel cylinder. The thionyl fluoride was made from thionyl chloride and sodium fluoride in acetonitrite according to the procedures as set forth in Journal of the American Chemical Society, vol. 84, p. 4275, 1962, and it was fluorinated to thionyl tetrafluoride using elemental fluorine. The alkali metal fluorides were fused and then powdered in a drybox prior to their use. The gaseous reactants were purified by fractional condensation.

EXAMPLE 1 Preparation of SF OCl: 3.32 g. of CsF powder (21.8 mmol) was loaded into a 30 ml. prepassivated cylinder in a drybox. After evacuation, somons cm. 18.4 mmol) and ClF (430 cmfi, 19.2. mmol) were separately condensed into the reactor at 196 C. The cold bath was changed to 78 C. and the reaction allowed to proceed overnight. The products of the reaction were separated by fractional condensation at 112 C. and 196 C. as the cylinder was warmed to ambient temperature. The trap cooled at -196 C. contained 37 cm. (1.65 mmol) which was identified by infrared examination as a mixture of unreacted ClF with minor quantities of 80R, and SP The high temperature fraction was pure, colorless SF OC1 (402 cm 17.9 mmol), 97 percent yield. The preparation of SF OCl was carried out using ClF in excess as its high volatility facilitated product separation.

in addition to the use of CsF, the catalytic activity of IQF was examined and it was found to be effective in forming SF OCl. In the absence of any added CsF or K F, no reaction between ClF and SOF occurred at either 78 C. or room temperature. Cesium fluoride appears to promote the formation of SF OCl more readily than KF. Thus, a synthesis of SF OCl (10 mmol scale) using CsF gave a 15 percent yield in 1 hour at 78" C. whereas KF produced a 13 percent yield in 2 hours.

The newly formed chloroxysulfurpentafiuoride is a clear, water white liquid and is stable for very limited periods at room temperature in clean, dry, prepassivated stainless steel or perhalogenated plastic equipment. Storage at 40 C. in stainless steel cylinders has resulted in only a few percent decomposition over a 3 4 week period. This decomposition can be limited to a negligible amount by low temperature storage in the presence of KF or CsF since the products of the decomposition are S01 1, and ClF, i.e., the starting materials. The molecular weight of SF OCl as determined by gas density was 177 (calculated 178.5). The vapor pressure of SF OCI over the tempera ture range -65 to 0 is [given as T K.), '1" (mm.)]: 208.5, 1 6; 225.3, 52; 241.7, 128; 245.4, 250.2, 186; 273.2, 520. The vapor pressure-temperature relationship is 3 described by the equation log P =7.576041324.37/T K. The normal boiling point calculated from the equation is 8.9 C., with a heat of vaporization of 6.06 Kcal./ mole and a Trouton constant of 21.5.

EXAMPLE 2 Prepartion of SF OOSF A sample of SF OCl (70.0 0111. 3.12 mmol) Was condensed at -196 into a Pyrex ampoule fitted with a stopcock (Halocarbon grease). The ampoule was warmed to room temperature and irradiated for 3 hours (Hanovia 100 watt utility lamp). Products of the photolysis were separated by several fractional condensations in traps cooled to 95 and -l96. Identification of the products was made from infrared spectra and mass spectra. The 196 C. trap contained 62.2 cm. (2.78 mmol) of a mixture consisting of 34 cm. C1 22 cm. SOF 5 cm. SiF and a small amount of 80 1 No unreacted SF OCl was observed. The high temperature fraction (23.0 cmfi, 1.02 mmol) was nearly pure SF OOSF The mass cracking pattern found for SF OOSF agreed with the pattern reported in Journal of the American Chemical Society, 83, 298, 1961. The principal ions observed: SF 100; SF OO+, 2.6; SF 2.4; SF O+, 92.0; SF OO+, 2.0; SE 27.0; SF O+, 19.2; SFOO+, 3.2; SF 12.0; SFO+, 20.0; SF+, 3.0; 80+, 3.5; S+, 7.8; 2.2.

EXAMPLE 3 Preparation of SF ONF A sample of SF OCl (105 cm. 4.69 mmol) was condensed into a 2.50 ml. Pyrex ampoule at 196 C. together with N F (47.3 cm. 2.11 mmol). After warming to room temperature the ampoule was irradiated for 3-5 minutes and recooled to 196 C. Subsequent fractionations through traps cooled to 112 C. and 196 C. gave SF ONF (14.0 cm. 0.62 mmol) in the high temperature trap. Identification of the SF ONF was based on its infrared spectrum (Inorganic Chemistry, 4, 1342, 1965) and vapor density. The low temperature trap contained a mixture (181 cm., 8.08 mmol), composed mostly of SOF and C1 with lesser amounts of N F and FNO. The yield of SF ONF was 14 percent.

EXAMPLE 4 Preparation of SF OC(O)Cl: Chloroxysulfurpentafluoride (127 cm. 5.67 mmol) was condensed into a 500 ml. Pyrex ampoule at 196 C. followed by approximately 150 cm. of CO (measured by pressure difference). As the ampoule was warming to ambient temperature it was irradiated for 25 minutes. Unreacted CO was pumped out of the ampoule after cooling to 196 C. and the contents were vacuum fractionated through traps cooled to 95 C. and 196 C. The latter fraction (20.8 cm. 0.93 mmol) was a mixture of SOF COFCl and a trace of SO F as indicated by an infrared spectrum. The95 C. fraction was pure SF OC(O)C1 (117 cmfi, 5.22 mmol), a 92 percent yield.

Pentafluorosulfur chloroformate is a water-clear liquid and a colorless gas. It is stable at room temperature in glass, stainless steel or Kel-F apparatus. The molecular weight of SF OC(O)Cl as determined by vapor density assuming ideal gas behavior was 202 (calculated 206.5). The vapor pressure of SF OC(O)Cl over the temperature range 64 C. to 23 C. is [given as T K.), P mm)]: 209.0, 3; 226.8, 12; 251.0, 54; 273.2, 128; 296.8, 319. The vapor pressure-temperature relationship is described by the equation log P =7.33542-1423.85/T K. The normal boiling point calculated from the equation is 46.4 C., with a heat a vaporization of 6.51 Kcal./m0le and a Trouton constant of 20.4.

In the accompanying drawing is set forth a schematic flow diagram illustrating the reaction employed within the spirit and scope of this invention. The flow diagram depicts SOFE reacting with ClF in the presence of an MP to give a SE 0 group. The SE 0 group can be reacted with CO, N F SE 0 or a compound containing an olefin bond to give compounds of the formula SF OR wherein R R is -CC10, NF OSF or --R;Cl and wherein R; is a perfiuoro alkylene radical.

The chloroxysulfurpentafluoride novel compound of the invention has been shown supra to possess utility for the production of pentafiuorosulfur chloroformate and other like compounds such as pentafiuorosulfurperoxide and pentafluorosulfur oxydifluoramine. The compounds chloroxysulfurpentafiuoride, pentafluorosulfur chloroformate, pentafluorosulfur peroxide and pentafluorosulfur oxydifluoramine also also can be used as polymerization initiators for fiuoroolefins such as polymerizing the monomer CFCICF to the polymer polychlorotrifiuoroethylene. The compounds can also be used as a taxogen in telomerization reactions. The chloroformate, pentafluorosulfur chloroformate may also be used as a flotation agent.

We claim:

1. Chloroxysulfurpentafluoride of the formula SF OCl.

2. Pentafiuorosulfur chloroformate of the formula SF OC(O)Cl.

3. A process for preparing chloroxysulfurpentafiuoride of the formula SF OCl comprising reacting chlorine monofluoride and thionyl tetrafluoride at a temperature from 40 to -78 C. in the presence of a member selected from the group consisting of potassium fluoride, rubidium fluoride and cesium fluoride to produce said chloroxysulfurpentafluoride.

References Cited UNITED STATES PATENTS 3,281,217 10/1966 Firty, Jr 23-356 OTHER REFERENCES Merrill et al.: Bis-(pentafluorosulfur) Peroxide, J. Am. Chem. Soc. 83, 298 (1961).

OSCAR R. VERTIZ, Primary Examiner H. S. MILLER, Assistant Examiner U.S. Cl. X.R. 260-543H 

